Transition metal complexes containing substituted imidazole carbene as ligands and their application in OLEDs

ABSTRACT

Compounds having a metal M complexed to a ligand L containing a substituted imidazole carbene group, which is represented Formula (I), below: 
                         
wherein ring B is a 5-member aromatic heterocyclic ring containing at least one heteroatom selected from the group consisting of N, O, and S; wherein ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; wherein R A  represents mono, di, tri, tetra substitutions or no substitution; wherein R 1  represents mono, di, or tri substitution or no substitution; wherein each R A , R 1  and R 2  is independently selected from various possible substituents; wherein Z 1  is nitrogen or carbon; and wherein the ligand is optionally linked with other ligands to comprise a tridentate, tetradentate, pentadentate or hexadentate ligand. Devices, such as organic light emitting devices (OLEDs) that comprise such compounds are also provided.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser. No. 61/673,634, filed Jul. 19, 2012, the entire contents of which are incorporated herein by reference.

JOINT RESEARCH AGREEMENT

The claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to a joint university corporation research agreement: Regents of the University of Michigan, Princeton University, University of Southern California, and the Universal Display Corporation. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.

FIELD OF THE INVENTION

The present invention relates to organic light emitting devices (OLEDs). More specifically, the invention relates to phosphorescent light emitting materials that may have improved operational lifetime.

BACKGROUND

Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.

OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Color may be measured using CIE coordinates, which are well known to the art.

One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)₃, which has the following structure:

In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.

As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.

As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.

As used herein, “solution processible” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.

As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.

As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.

More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.

SUMMARY OF THE INVENTION

A new type of light emitting material is provided. This new class of material includes compounds having a metal M₁ complexed to a ligand L₃ containing a substituted imidazole carbene group, which is represented Formula (I), below:

wherein ring B is a 5-member aromatic heterocyclic ring containing at least one heteroatom selected from the group consisting of N, O, and S; wherein ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; wherein R_(A) represents mono, di, tri, tetra substitutions or no substitution; wherein R₁ represents mono, di, or tri substitution or no substitution; wherein each R_(A), R₁ and R₂ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two adjacent substituents are optionally joined to form a ring, which can be further substituted; wherein Z₁ is nitrogen or carbon; and wherein the ligand L₃ is optionally linked with other ligands to comprise a tridentate, tetradentate, pentadentate or hexadentate ligand.

Any suitable metal M₁ can be used in the above complexes. In some embodiments, the ligand L₃ is complexed to a metal selected from the group consisting of: Ir, Rh, Re, Ru, Os, Pt, Au, and Cu. In some further embodiments, the metal M₁ in the complex is Ir or Pt.

In some further embodiments, the complex comprises a ligand L₃ that is selected from the group consisting of:

wherein A₁, A₂, and A₃ are independently selected from the group consisting of carbon, nitrogen, oxygen, and sulfur, and at least one of A₁, A₂, and A₃ is not carbon. Other variables have the definitions provided above.

In some further such embodiments, the complex comprises a ligand L₃ that is selected from the group consisting of:

wherein A₁ and A₃ are independently selected from the group consisting of oxygen, nitrogen, and sulfur; wherein R₃ represents mono, di, tri, or tetra substitution, or no substitution; and wherein R₃ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein any two adjacent substituents are optionally joined to form into a ring, which can be further substituted. Other variables have the definitions provided above.

In some further such embodiments, the complex comprises a ligand L₃ that is selected from the group consisting of:

Substituted imidazole carbene complexes of Formula (II) are also provided:

wherein -L₁-L₂- is a bidentate ligand selected from the group consisting of:

wherein R_(a), R_(b), and R_(c) represent mono, di, tri or tetra substitutions; wherein R_(a), R_(b), and R_(c) are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein any two adjacent substituents of R_(a), R_(b), and R_(c) are optionally joined to form a ring, which can be further substituted; and wherein n is 1, 2 or 3. Other variables have the definitions provided above.

Substituted imidazole carbene complexes of Formula (III) are also provided:

wherein -L₁-L₂- is a bidentate ligand; and wherein m is 1 or 2. Other variables have the definitions provided above.

Substituted imidazole carbene complexes of Formula (IV) are also provided:

wherein -L₁-L₂- is a bidentate ligand; and wherein X is selected from a group consisting of O, S, NR, CR′R″, SiR′R″; wherein R, R′, and R″ are independently selected from the group consisting of alkyl, aryl and heteroaryl, wherein R′ and R″ are optionally linked; and wherein any two adjacent substituents are optionally joined to form into a ring, which can be further substituted. Other variables have the definitions provided above.

Substituted imidazole carbene complexes of Formula (V) are also provided:

where the variables have the definitions provided above.

Substituted imidazole carbene complexes of Formula (VI) are also provided:

wherein X and Y are independently selected from a group consisting of O, S, NR, CR′R″, and SiR′R″; and wherein R, R′, and R″ are independently selected from the group consisting of alkyl, aryl, and heteroaryl; and wherein any two adjacent substituents are optionally joined to form into a ring, which can be further substituted. The other variables have the definitions provided above.

Substituted imidazole carbene complexes of Formula (VII) are also provided:

where the variables have the definitions provided above.

Substituted imidazole carbene complexes are provided, where the complexes are selected from the group consisting of:

Substituted imidazole carbene complexes are provided, where the complexes are selected from the group consisting of:

A device is also provided. The device may include an anode, a cathode, and an organic layer disposed between the anode and the cathode, where the organic layer comprises a compound of any of the foregoing embodiments (e.g., a substituted imidazole carbene complex).

The invention is not limited to any particular type of device. In some embodiments, the device is a consumer product. In some embodiments, the device is an organic light emitting device (OLED). In other embodiments, the device comprises a lighting panel.

In some embodiments, the organic layer of the device is an emissive layer. In some such embodiments, the substituted imidazole carbene complex is an emissive dopant. In some other embodiments, the substituted imidazole carbene complex is a non-emissive dopant.

In some embodiments, the organic layer of the device further comprises a host.

In some such embodiments, the host comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan, wherein any substituent in the host is an unfused substituent independently selected from the group consisting of C_(n)H_(2n+1), OC_(n)H_(2n+1), OAr₁, N(C_(n)H_(2n+1))₂, N(Ar₁)(Ar₂), CH═CH—C_(n)H_(2n+1), C≡C—C_(2n+1), Ar₁, Ar₁ 13 Ar₂, C_(n)H_(2n)—Ar₁, or no substitution, wherein n is from 1 to 10, and wherein Ar₁ and Ar₂ are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. In some such embodiments, the host is a compound selected from the group consisting of:

and combinations thereof.

In some other embodiments, the host comprises a metal complex. In some further embodiments, the host comprises at least one of the chemical groups selected from the group consisting of carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.

FIG. 3 shows a chemical formula representing a substituted imidazole carbene ligand as disclosed herein.

DETAILED DESCRIPTION

Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.

More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-1”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.

FIG. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.

More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F.sub.4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an “inverted” OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.

Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.

Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. patent application Ser. No. 10/233,470, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processibility than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.

Devices fabricated in accordance with embodiments of the invention may be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads up displays, fully transparent displays, flexible displays, laser printers, telephones, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.).

The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.

The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, arylkyl, heterocyclic group, aryl, aromatic group, and heteroaryl are known to the art, and are defined in U.S. Pat. No. 7,279,704 at cols. 31-32, which are incorporated herein by reference.

Metal carbene complexes have a wide triplet energy gap, which makes them suitable as blue emitters in phosphorescent OLEDs. However, these complexes can exhibit instability when employed in certain devices, thereby leading to reduced operation lifetime. Without being bound by theory, it is believed that such instability may be attributable to a variety of factors, including, but not limited to, long excitation delay lifetime, a mismatch of energy levels, and unbalanced electron/hole fluexes. Substitution on the imidazole-carbene moiety can affect the complex's HOMO/LUMO energy levels, its emission spectrum, and its emission quantum yield, thereby allowing one to fine-tune energy levels, emission spectra, and charge transport properties.

New metal complexes are provided, where the metal is complexed to at least one ligand that contains a substituted imidazole carbene moiety. Such complexes may be advantageously used in OLEDs. Particular substituted imidazole carbene complexes are compounds comprising a metal M₁ complexed to a ligand L₃ of Formula (I):

wherein ring B is a 5-member aromatic heterocyclic ring containing at least one heteroatom selected from the group consisting of N, O, and S; wherein ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; wherein R_(A) represents mono, di, tri, tetra substitutions or no substitution; wherein R₁ represents mono, di, or tri substitution or no substitution; wherein each R_(A), R₁ and R₂ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two adjacent substituents are optionally joined to form a ring, which can be further substituted; wherein Z₁ is nitrogen or carbon; and wherein the ligand L₃ is optionally linked with other ligands to comprise a tridentate, tetradentate, pentadentate or hexadentate ligand.

Any suitable metal M₁ can be used in the above complexes. In some embodiments, the ligand L₃ is complexed to a metal M selected from the group consisting of: Ir, Rh, Re, Ru, Os, Pt, Au, and Cu. In some further embodiments, the metal M₁ in the complex is Ir or Pt.

In some further embodiments, the complex comprises a ligand L₃ that is selected from the group consisting of:

wherein A₁, A₂, and A₃ are independently selected from the group consisting of carbon, nitrogen, oxygen, and sulfur, and at least one of A₁, A₂, and A₃ is not carbon. Other variables have the definitions provided above.

In some further such embodiments, the complex comprises a ligand L₃ that is selected from the group consisting of:

wherein A₁ and A₃ are independently selected from the group consisting of oxygen, nitrogen, and sulfur; wherein R₃ represents mono, di, tri, or tetra substitution, or no substitution; and wherein R₃ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein any two adjacent substituents are optionally joined to form into a ring, which can be further substituted. Other variables have the definitions provided above.

In some further such embodiments, the complex comprises a ligand L₃ that is selected from the group consisting of:

Substituted imidazole carbene complexes of Formula (II) are also provided.

wherein -L₁-L₂- is a bidentate ligand selected from the group consisting of:

wherein R_(a), R_(b), and R_(c) represent mono, di, tri or tetra substitutions; wherein R_(a), R_(b), and R_(c) are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein any two adjacent substituents of R_(a), R_(b), and R_(c) are optionally joined to form a ring, which can be further substituted; and wherein n is 1, 2 or 3. Other variables have the definitions provided above.

Substituted imidazole carbene complexes of Formula (III) are also provided:

wherein -L₁-L₂- is a bidentate ligand; and wherein m is 1 or 2. Other variables have the definitions provided above.

Substituted imidazole carbene complexes of Formula (IV) are also provided:

wherein -L₁-L₂- is a bidentate ligand; and wherein X is selected from a group consisting of O, S, NR, CR′R″, SiR′R″; wherein R, R′, and R″ are independently selected from the group consisting of alkyl, aryl and heteroaryl, wherein R′ and R″ are optionally linked; and wherein any two adjacent substituents are optionally joined to form into a ring, which can be further substituted. Other variables have the definitions provided above.

Substituted imidazole carbene complexes of Formula (V) are also provided:

where the variables have the definitions provided above.

Substituted imidazole carbene complexes of Formula (VI) are also provided:

wherein X and Y are independently selected from a group consisting of O, S, NR, CR′R″, and SiR′R″; and wherein R, R′, and R″ are independently selected from the group consisting of alkyl, aryl, and heteroaryl; and wherein any two adjacent substituents are optionally joined to form into a ring, which can be further substituted. The other variables have the definitions provided above.

Substituted imidazole carbene complexes of Formula (VII) are also provided:

where the variables have the definitions provided above.

Substituted imidazole carbene complexes are provided, where the complexes are selected from the group consisting of:

Substituted imidazole carbene complexes are provided, where the complexes are selected from the group consisting of:

A device is also provided. The device may include an anode, a cathode, and an organic layer disposed between the anode and the cathode, where the organic layer comprises a compound of any of the foregoing embodiments (e.g., a substituted imidazole carbene complex).

The invention is not limited to any particular type of device. In some embodiments, the device is a consumer product. In some embodiments, the device is an organic light emitting device (OLED). In other embodiments, the device comprises a lighting panel.

In some embodiments, the organic layer of the device is an emissive layer. In some such embodiments, the substituted imidazole carbene complex is an emissive dopant. In some other embodiments, the substituted imidazole carbene complex is a non-emissive dopant.

In some embodiments, the organic layer of the device further comprises a host.

In some such embodiments, the host comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan, wherein any substituent in the host is an unfused substituent independently selected from the group consisting of C_(n)H_(2n+1), OC_(n)H_(2n+1), OAr₁, N(C_(n)H_(2n+1))₂, N(Ar₁)(Ar₂), CH═CH—C_(n)H_(2n+1), C≡C—C_(n)H_(2n+1), Ar₁, Ar₁—Ar₂, C_(n)H_(2n)—Ar₁, or no substitution, wherein n is from 1 to 10, and wherein Ar₁ and Ar₂ are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. In some such embodiments, the host is a compound selected from the group consisting of:

and combinations thereof.

In some other embodiments, the host comprises a metal complex. In some further embodiments, the host comprises at least one of the chemical groups selected from the group consisting of carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

Combination with Other Materials

The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, compounds disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but not limit to: a phthalocyanine or porphryin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoO_(x); a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.

Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:

Each of Ar¹ to Ar⁹ is selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each Ar is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, Ar¹ to Ar⁹ is independently selected from the group consisting of:

k is an integer from 1 to 20; X¹ to X⁸ is C (including CH) or N; Ar¹ has the same group defined above.

Examples of metal complexes used in HIL or HTL include, but not limit to the following general formula:

M is a metal, having an atomic weight greater than 40; (Y¹-Y²) is a bidentate ligand, Y¹ and Y² are independently selected from C, N, O, P, and S; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and m+n is the maximum number of ligands that may be attached to the metal.

In one aspect, (Y¹-Y²) is a 2-phenylpyridine derivative.

In another aspect, (Y¹-Y²) is a carbene ligand.

In another aspect, M is selected from Ir, Pt, Os, and Zn.

In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc⁺/Fc couple less than about 0.6 V.

In addition to the host materials described above, the device may further comprise other host materials. Examples of such other host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. While the Table below categorizes host materials as preferred for devices that emit various colors, any host material may be used with any dopant so long as the triplet criteria are satisfied.

Examples of metal complexes used as host are preferred to have the following general formula:

M is a metal; (Y³-Y⁴) is a bidentate ligand, Y³ and Y⁴ are independently selected from C, N, O, P, and S; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and m+n is the maximum number of ligands that may be attached to the metal.

In one aspect, the metal complexes are:

(O—N) is a bidentate ligand, having metal coordinated to atoms O and N.

In another aspect, M is selected from Ir and Pt.

In a further aspect, (Y³-Y⁴) is a carbene ligand.

Examples of organic compounds used as host are selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each group is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, host compound contains at least one of the following groups in the molecule:

R¹ to R⁷ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above; k is an integer from 0 to 20; X¹ to X⁸ are selected from C (including CH) or N; and Z¹ and Z² are selected from NR¹, O, or S.

A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED.

In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.

In another aspect, compound used in HBL contains at least one of the following groups in the molecule:

k is an integer from 0 to 20; L is an ancillary ligand, m is an integer from 1 to 3.

Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.

In one aspect, compound used in ETL contains at least one of the following groups in the molecule:

R¹ is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above; Ar¹ to Ar^(a) has the similar definition as Ar's mentioned above; k is an integer from 0 to 20; X¹ to X⁸ is selected from C (including CH) or N.

In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:

(O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal.

In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also encompass undeuterated, partially deuterated, and fully deuterated versions thereof.

In addition to and/or in combination with the materials disclosed herein, many hole injection materials, hole transporting materials, host materials, dopant materials, exiton/hole blocking layer materials, electron transporting and electron injecting materials may be used in an OLED. Non-limiting examples of the materials that may be used in an OLED in combination with materials disclosed herein are listed in Table 1 below. Table 1 lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.

TABLE 1 MATERIAL EXAMPLES OF MATERIAL PUBLICATIONS Hole injection materials Phthalocyanine and porphryin compounds

Appl. Phys. Lett. 69, 2160 (1996) Starburst triarylamines

J. Lumin. 72-74, 985 (1997) CF_(x) Fluoro- hydrocarbon polymer

Appl. Phys. Lett. 78, 673 (2001) Conducting polymers (e.g., PEDOT:PSS, polyaniline, polypthiophene)

Synth. Met. 87, 171 (1997) WO2007002683 Phosphonic acid and sliane SAMs

US20030162053 Triarylamine or polythiophene polymers with conductivity dopants

 

 

EP1725079A1 Organic compounds with conductive inorganic compounds, such as molybdenum and tungsten oxides

US20050123751 SID Symposium Digest, 37, 923 (2006) WO2009018009 n-type semiconducting organic complexes

US20020158242 Metal organometallic complexes

US20060240279 Cross-linkable compounds

US20080220265 Polythiophene based polymers and copolymers

WO 2011075644 EP2350216 Hole transporting materials Triarylamines (e.g., TPD, α-NPD)

Appl. Phys. Lett. 51, 913 (1987)

US5061569

EP650955

J. Mater. Chem. 3, 319 (1993)

Appl. Phys. Lett. 90, 183503 (2007)

Appl. Phys. Lett. 90, 183503 (2007) Triaylamine on spirofluorene core

Synth. Met. 91, 209 (1997) Arylamine carbazole compounds

Adv. Mater. 6, 677 (1994), US20080124572 Triarylamine with (di)benzothiophene/ (di)benzo- furan

US20070278938, US20080106190 US20110163302 Indolocarbazoles

Synth. Met. 111, 421 (2000) Isoindole compounds

Chem. Mater. 15, 3148 (2003) Metal carbene complexes

US20080018221 Phosphorescent OLED host materials Red hosts Arylcarbazoles

Appl. Phys. Lett. 78, 1622 (2001) Metal 8-hydroxy- quinolates (e.g., Alq₃, BAlq)

Nature 395, 151 (1998)

US20060202194

WO2005014551

WO2006072002 Metal phenoxy- benzothiazole compounds

Appl. Phys. Lett. 90, 123509 (2007) Conjugated oligomers and polymers (e.g., polyfluorene)

Org. Electron. 1, 15 (2000) Aromatic fused rings

WO2009066779, WO2009066778, WO2009063833, US20090045731, US20090045730, WO2009008311, US20090008605, US20090009065 Zinc complexes

WO2010056066 Chrysene based compounds

WO2011086863 Green hosts Arylcarbazoles

Appl. Phys. Lett. 78, 1622 (2001)

US20030175553

WO2001039234 Aryltriphenylene compounds

US20060280965

US20060280965

WO2009021126 Poly-fused heteroaryl compounds

US20090309488 US20090302743 US20100012931 Donor acceptor type molecules

WO2008056746

WO2010107244 Aza-carbazole/ DBT/DBF

JP2008074939

US20100187984 Polymers (e.g., PVK)

Appl. Phys. Lett. 77, 2280 (2000) Spirofluorene compounds

WO2004093207 Metal phenoxy- benzooxazole compounds

WO2005089025

WO2006132173

JP200511610 Spirofluorene- carbazole compounds

JP2007254297

JP2007254297 Indolocabazoles

WO2007963796

WO2007063754 5-member ring electron deficient heterocycles (e.g., triazole, oxadiazole)

J. Appl. Phys. 90, 5048 (2001)

WO2004107822 Tetraphenylene complexes

US20050112407 Metal phenoxypyridine compounds

WO2005030900 Metal coordination complexes (e.g., Zn, Al with N{circumflex over ( )}N ligands)

US20040137268, US20040137267 Blue hosts Arylcarbazoles

Appl. Phys. Lett, 82, 2422 (2003)

US20070190359 Dibenzothiophene/ Dibenzo- furan-carbazole compounds

WO2006114966, US20090167162

US20090167162

WO2009086028

US20090030202, US20090017330

US20100084966 Silicon aryl compounds

US20050238919

WO2009003898 Silicon/ Germanium aryl compounds

EP2034538A Aryl benzoyl ester

WO2006100298 Carbazole linked by non- conjugated groups

US20040115476 Aza-carbazoles

US20060121308 High triplet metal organometallic complex

US7154114 Phosphorescent dopants Red dopants Heavy metal porphyrins (e.g., PtOEP)

Nature 395, 151 (1998) Iridium(III) organometallic complexes

Appl. Phys. Lett. 78, 1622 (2001)

US2006835469

US2006835469

US20060202194

US20060202194

US20070087321

US20080261076 US20100090591

US20070087321

Adv. Mater. 19, 739 (2007)

WO2009100991

WO2008101842

US7232618 Platinum(II) organometallic complexes

WO2003040257

US20070103060 Osminum(III) complexes

Chem. Mater. 17, 3532 (2005) Ruthenium(II) complexes

Adv. Mater. 17, 1059 (2005) Rhenium (I), (II), and (III) complexes

US20050244673 Green dopants Iridium(III) organometallic complexes

Inorg. Chem. 40, 1704 (2001)

US20020034656

US7332232

US20090108737

WO2010028151

EP1841834B

US20060127696

US20090039776

US6921915

US20100244004

US6687266

Chem. Mater. 16, 2480 (2004)

US20070190359

US 20060008670 JP2007123392

WO2010086089, WO2011044988

Adv. Mater. 16, 2003 (2004)

Angew. Chem. Int. Ed. 2006, 45, 7800

WO2009050290

US20090165846

US20080015355

US20010015432

US20100295032 Monomer for polymeric metal organometallic compounds

US7250226, US7396598 Pt(II) organometallic complexes, including polydentated ligands

Appl. Phys. Lett. 86, 153505 (2005)

Appl. Phys. Lett. 86, 153505 (2005)

Chem. Lett. 34, 592 (2005)

WO2002015645

US20060263635

US20060182992 US20070103060 Cu complexes

WO2009000673

US20070111026 Gold complexes

Chem. Commun. 2906 (2005) Rhenium(III) complexes

Inorg. Chem. 42, 1248 (2003) Osmium(II) complexes

US7279704 Deuterated organometallic complexes

US20030138657 Organometallic complexes with two or more metal centers

US20030152802

US7090928 Blue dopants Iridium(III) organometallic complexes

WO2002002714

WO2006009024

US20060251923 US20110057559 US20110204333

US7393599, WO2006056418, US20050260441, WO2005019373

US7534505

WO2011051404

US7445855

US20070190359, US20080297033 US20100148663

US7338722

US20020134984

Angew. Chem. Int. Ed. 47, 1 (2008)

Chem. Mater. 18, 5119 (2006)

Inorg. Chem. 46, 4308 (2007)

WO2005123873

WO2005123873

WO2007004380

WO2006082742 Osmium(II) complexes

US7279704

Organo- metallics 23, 3745 (2004) Gold complexes

Appl. Phys. Lett. 74, 1361 (1999) Platinum(II) complexes

WO2006098120, WO2006103874 Pt tetradentate complexes with at least one metal- carbene bond

US7655323 Exciton/hole blocking layer materials Bathocuprine compounds (e.g., BCP, BPhen)

Appl. Phys. Lett. 75, 4 (1999)

Appl. Phys. Lett. 79, 449 (2001) Metal 8- hydroxyquinolates (e.g., BAlq)

Appl. Phys. Lett. 81, 162 (2002) 5-member ring electron deficient heterocycles such as triazole, oxadiazole, imidazole, benzoimidazole

Appl. Phys. Lett. 81, 162 (2002) Triphenylene compounds

US20050025993 Fluorinated aromatic compounds

Appl. Phys. Lett. 79, 156 (2001) Phenothiazine- S-oxide

WO2008132085 Silylated five-membered nitrogen, oxygen, sulfur or phosphorus dibenzoheterocycles

WO2010079051 Aza-carbazoles

US20060121308 Electron transporting materials Anthracene- benzoimidazole compounds

WO2003060956

US20090179554 Aza triphenylene derivatives

US20090115316 Anthracene- benzothiazole compounds

Appl. Phys. Lett. 89, 063504 (2006) Metal 8- hydroxyquinolates (e.g., Alq₃, Zrq₄)

Appl. Phys. Lett. 51, 913 (1987) US7230107 Metal hydroxybeno- quinolates

Chem. Lett. 5, 905 (1993) Bathocuprine compounds such as BCP, BPhen, etc

Appl. Phys. Lett. 91, 263503 (2007)

Appl. Phys. Lett. 79, 449 (2001) 5-member ring electron deficient heterocycles (e.g., triazole, oxadiazole, imidazole, benzoimidazole)

Appl. Phys. Lett. 74, 865 (1999)

Appl. Phys. Lett. 55, 1489 (1989)

Jpn. J. Apply. Phys. 32, L917 (1993) Silole compounds

Org. Electron. 4, 113 (2003) Arylborane compounds

J. Am. Chem. Soc. 120, 9714 (1998) Fluorinated aromatic compounds

J. Am. Chem. Soc. 122, 1832 (2000) Fullerene (e.g., C60)

US20090101870 Triazine complexes

US20040036077 Zn (N{circumflex over ( )}N) complexes

US6528187

EXPERIMENTAL Compound Examples

Some of the substituted imidazole carbene complexes were synthesized as follows.

Synthesis of Compound 1.

Iridium Heteroleptic Compound

Into a solution of 3-bromobenzo[b]thiophene (40 g, 190 mmol) in glacial acetic acid (140 ml) was added a solution of nitric acid (74 ml, 1760 mmol) in glacial acetic acid (40 mL) over a period of 45 min. The reaction mixture was stirred at room temperature for 5 hours before quenching with water. The precipitate was isolated by filtration, washed with water and recrystallized from ethyl acetate/hexane (1/1, v/v) to yield 3-bromo-2-nitrobenzo[b]thiophene (35 g, 72%) as yellow crystals.

A mixture solution of 3-bromo-2-nitrobenzo[b]thiophene (14 g, 54 mmol), aniline (14 ml, 154 mmol) and triethylamine (11 ml, 79 mmol) in DMF (150 ml) was heated at 120° C. for 30 min before quenching with water. The solid was isolated by filtration, washed with water and recrystallized from DCM/hexane to yield 2-nitro-N-phenylbenzo[b]thiophen-3-amine (14 g, 96%) as a yellow solid.

Into a solution of 2-nitro-N-phenylbenzo[b]thiophen-3-amine (13 g, 48 mmol) in acetic acid (200 ml) and water (20 ml) was added portionwise iron powder (14 g, 250 mmol). After stirring at room temperature for 2 h, it was filtered through a short plug of Celite and washed with DCM. The combined filtrate was washed with water and aqueous sodium carbonate solution. Upon evaporation off the solvent, the residue was purified by column chromatography on silica gel with hexane/DCM (4/1, v/v) as eluent to yield N³-phenylbenzo[b]thiophene-2,3-diamine (7.5 g, 65%) as a white solid.

Into a solution of N³-phenylbenzo[b]thiophene-2,3-diamine (16 g, 66.7 mmol) in trimethoxymethane (200 ml) was added formic acid (1.5 ml, 42.3 mmol) at room temperature. The reaction mixture was subsequently heated at 120° C. for 6 h. After cooling to room temperature, it was quenched with aqueous NaHCO₃ solution and extracted with ethyl acetate. Upon evaporation off the solvent, the residue was purified by chromatography on silica gel with hexane/EtOAc (95/5, v/v) as eluent to yield 1-phenyl-1H-benzo[4,5]thieno[2,3-d]imidazole (9.0 g, 54%) as a solid.

A solution of 1-phenyl-1H-benzo[4,5]thieno[2,3-d]imidazole (4 g, 16 mmol) and methyl iodide (11.36 g, 80 mmol) in EtOAc (100 ml) was stirred for 48 h at room temperature. The precipitate was isolated by filtration and washed thoroughly with EtOAc to yield 3-methyl-1-phenyl-1H-benzo[4,5]thieno[2,3-d]imidazol-3-ium iodide (5.52 g, 88%) as a white solid.

A mixture of 3-methyl-1-phenyl-1H-benzo[4,5]thieno[2,3-d]imidazol-3-ium iodide (2.5 g, 6.37 mmol) and Ag₂O (0.738 g, 3.19 mmol) in acetonitrile (150 ml) was stirred at room temperature under nitrogen overnight. Upon evaporation off the solvent, dimer (3.16 g, 1.89 mmol) and THF (150 ml) was introduced and the reaction mixture was refluxed under nitrogen overnight. After cooling to room temperature, it was filtered through a short plug of Celite and the solid was washed with DCM. The combined filtrate was evaporated and purified by column chromatography on TEA-treated silica gel with hexane/DCM (9/1, v/v) as eluent as eluent to yield the mer form of the Ir heteroleptic compound (3.0 g, 75%) as a yellow solid.

The mer form of the product (2.0 g, 1.88 mmol) was dissolved in DMSO (150 ml) and irradiated with UV light (360 nm) under nitrogen for 2 h. Upon evaporation off the solvent under reduced pressure, the residue was purified by column chromatography on TEA-treated silica gel with hexane as eluent followed by extraction successively with hexane and methanol to yield the fac form of the product (1.4 g, 70%) as a yellow solid, identified as Compound 1.

Computational Examples

Compound 1 and comparative compound (CC-1) were subjected to DFT computational investigation using the Gaussian software package at the B3LYP/cep-31 g functional and basis set. It was found that Compound 1 has a triplet energy (T1) of 2.67 eV (464 nm), which will emit a blue color, whereas CC-1 has a T1 of 2.24 eV (552 nm), which will emit a yellow color. The enhanced T1 of Compound 1 is attributable to the 5-membered heterocycle thieno ring fused to the imidazole ring. On the other hand, CC-1 has a phenyl ring fused to the imidazole ring, leading to lower triplet energy. Since a high triplet energy is beneficial for emission in shorter wavelength region, it is concluded that metal complexes containing ligand of Formula I are advantageous over those that do not have the 5-membered heterocycle rings.

Device Examples Example 1

An example device was fabricated by high vacuum (<10⁻⁷ Torr) thermal evaporation (VTE). The anode electrode is 800 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of UF followed by 1,000 Å of Al. The device was encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H₂O and O₂) immediately after fabrication, and a moisture getter was incorporated inside the package.

The organic stack of the OLED device used has the following structure: from the ITO surface, 100 Å of LG101 (LG Chem) as the hole injection layer, 300 Å of NPD doped with 2 weight percent of Alq as the hole transporting layer (HTL), 300 Å of Compound H doped with 15 weight percent of Compound 1 as the emissive layer (EML), 50 Å of Compound H as the Blocking Layer (BL) and 400 Å of Alq as the electron transport layer (ETL).

Under a driving voltage of 7.4 V, the device achieves a current density of 10 mA/cm² and a sky-blue emission with 1931 CIE coordinate of (0.195, 0.322) and a current efficiency of 0.8 cd/A.

It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting. 

We claim:
 1. A compound comprising a ligand L₃ of Formula (I):

wherein ring B is a 5-member aromatic heterocyclic ring containing at least one heteroatom selected from the group consisting of N, O, and S; wherein ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; wherein R_(A) represents mono, di, tri, tetra substitutions or no substitution; wherein R₁ represents mono, di, or tri substitution or no substitution; wherein each R_(A), R₁ and R₂ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two adjacent substituents are optionally joined to form a ring, which can be further substituted; wherein Z₁ is nitrogen or carbon; wherein the ligand L₃ is coordinated to a metal M₁; and wherein the ligand L₃ is optionally linked with other ligands to comprise a tridentate, tetradentate, pentadentate or hexadentate ligand.
 2. The compound of claim 1, wherein M₁ is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Au, and Cu.
 3. The compound of claim 1, wherein M₁ is Ir or Pt.
 4. The compound of claim 1, wherein ligand L₃ is selected from the group consisting of:

wherein A₁, A₂, and A₃ are independently selected from the group consisting of carbon, nitrogen, oxygen, and sulfur, and at least one of A₁, A₂, and A₃ is not carbon.
 5. The compound of claim 4, wherein the ligand L₃ is selected from the group consisting of:

wherein A₁ and A₃ are independently selected from the group consisting of oxygen, nitrogen, and sulfur; wherein R₃ represents mono, di, tri, or tetra substitution, or no substitution; and wherein R₃ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein any two adjacent substituents are optionally joined to form into a ring, which can be further substituted.
 6. The compound of claim 5, wherein the ligand L₃ is selected from the group consisting of:


7. The compound of claim 1, where the compound is a compound of Formula (II):

wherein -L₁-L₂- is a bidentate ligand selected from the group consisting of:

wherein R_(a), R_(b), and R_(c) represent mono, di, tri or tetra substitutions; wherein R_(a), R_(b), and R_(c) are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein any two adjacent substituents of R_(a), R_(b), and R_(c) are optionally joined to form a ring, which can be further substituted; and wherein n is 1, 2 or
 3. 8. The compound of claim 1, wherein the compound is a compound of Formula (III):

wherein -L₁-L₂- is a bidentate ligand; and wherein m is 1 or
 2. 9. The compound of claim 8, wherein the compound is a compound of Formula (IV):

wherein -L₁-L₂- is a bidentate ligand; and wherein X is selected from a group consisting of O, S, NR, CR′R″, SiR′R″; wherein R, R′, and R″ are independently selected from the group consisting of alkyl, aryl and heteroaryl, wherein R′ and R″ are optionally linked; and wherein any two adjacent substituents are optionally joined to form into a ring, which can be further substituted.
 10. The compound of claim 9, wherein the compound is a compound of Formula (V):


11. The compound of claim 1, wherein the compound is a compound of Formula (VI):

wherein X and Y are independently selected from a group consisting of O, S, NR, CR′R″, and SiR′R″; and wherein R, R′, and R″ are independently selected from the group consisting of alkyl, aryl, and heteroaryl; and wherein any two adjacent substituents are optionally joined to form into a ring, which can be further substituted.
 12. The compound of claim 11, wherein the compound is a compound of Formula (VII):


13. The compound of claim 1, wherein the compound is selected from the group consisting of:


14. The compound of claim 1, wherein the compound is selected from the group consisting of:


15. A first device comprising a first organic light emitting device, further comprising: an anode; a cathode; and an organic layer, disposed between the anode and the cathode, comprising a compound comprising a ligand L₃ of Formula (I):

wherein ring B is a 5-member aromatic heterocyclic ring containing at least one heteroatom selected from the group consisting of N, O, and S; wherein ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; wherein R_(A) represents mono, di, tri, tetra substitutions or no substitution; wherein R₁ represents mono, di, or tri substitution or no substitution; wherein each R_(A), R₁ and R₂ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two adjacent substituents are optionally joined to form a ring, which can be further substituted; wherein Z₁ is nitrogen or carbon; wherein the ligand L₃ is coordinated to a metal M₁; and wherein the ligand L₃ is optionally linked with other ligands to comprise a tridentate, tetradentate, pentadentate or hexadentate ligand.
 16. The first device of claim 15, wherein the first device is a consumer product.
 17. The first device of claim 15, wherein the first device is an organic light-emitting device.
 18. The first device of claim 15, wherein the first device comprises a lighting panel.
 19. The first device of claim 15, wherein the organic layer is an emissive layer and the compound is an emissive dopant.
 20. The first device of claim 15, wherein the organic layer is an emissive layer and the compound is a non-emissive dopant.
 21. The first device of claim 15, wherein the organic layer further comprises a host.
 22. The first device of claim 21, wherein the host comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan; wherein any substituent in the host is an unfused substituent independently selected from the group consisting of C_(n)H_(2n+1), OC_(n)H_(2n+1), OAr₁, N(C_(n)H_(2n+1))₂, N(Ar₁)(Ar₂), CH═CH—C_(n)H_(2n+1), C≡C—C_(n)H_(2n+1), Ar₁, Ar₁-Ar₂, C_(n)H_(2n)—Ar₁, or no substitution; wherein n is from 1 to 10; and wherein Ar₁ and Ar₂ are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.
 23. The first device of claim 21, wherein the host is selected from the group consisting of:

and combinations thereof.
 24. The first device of claim 21, wherein the host comprises a metal complex.
 25. The first device of claim 21, wherein the host comprises at least one of the chemical groups selected from the group consisting of carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. 